Dihydroperoxidation facilitates the conversion of lipids to aldehydic products via alkoxyl radicals

The mechanisms of formation of many aldehydic lipid oxidation products remain unclear, and the involvement of peroxyl radical additions in some cases was recently suggested. Here, the effect of α-tocopherol, a peroxyl radical trap, on the formation of aldehydic phospholipids from a phosphatidylcholine hydroperoxide was studied by electrospray ionization mass spectroscopy (ESI-MS). Based on the observed differential enhancement or suppression of formation of different aldehydes, new pathways are deduced for aldehyde formation via alkoxyl radicals derived from dihydroperoxy derivatives.     

Effects of Glycogen on Ceramide Production in Cultured Human Keratinocytes via Acid Sphingomyelinase Activation

Glycogen is a highly branched storage polysaccharide found mainly in the liver and the muscles. Glycogen is also present in the skin, but its functional role is poorly understood. Recently, it has been reported that glycogen plays an important role in intracellular signal transduction. In the epidermis of the skin, keratinocytes are the predominant cells that produce ceramide. Ceramides are lipids composed of sphingosine, and prevent water loss, as well as protecting the skin against environmental stressors. In this study, we investigated the effects of glycogen on ceramide production in cultured keratinocytes. Thin-layer chromatography revealed that incubation of keratinocytes with 2 % glycogen enhanced the cellular amount of ceramide NS (ceramide 2) by 3.4-fold compared to the control. We also found that glycogen regulated the mRNA expression levels of signaling molecules of the sphingomyelin-ceramide pathway by quantitative real-time PCR. The activity of sphingomyelinase was also significantly enhanced by 2.5-fold in cultures with 1 % glycogen compared to the control. Moreover, glycogen increased the ATP production by 1.5-fold compared to the control, while glucose did not affect the production. Western blotting showed that phosphorylation of Akt, a cellular signaling molecule, was inhibited in the presence of glycogen in cultured keratinocytes. This study shows that glycogen upregulates the ceramide production pathway from sphingomyelin in epidermal keratinocytes, and provides new insights into the role of glycogen in cellular signal transduction.     

Anti-Proliferative Activities and Apoptosis Induction by Triterpenes Derived from Eriobotrya japonica in Human Leukemia Cell Lines

Eriobotrya japonica leaf is a traditional herbal medicine that contains numerous triterpenes, which have various pharmacological properties. In this study, we investigated the anti-proliferative activity of four triterpenes derived from E. japonica, including corosolic acid (CA), ursolic acid (UA), maslinic acid (MA) and oleanolic acid (OA), in human leukemia cell lines. CA showed the strongest anti-proliferative activity in all of the leukemia cell lines tested, but not in normal human skin fibroblast cell lines. To determine the mechanism underlying the anti-proliferative effect of CA, we examined the effect of CA on molecular events known as apoptosis induction. CA induced chromatin condensation, DNA fragmentation, sub-G₁ phase DNA, activation of caspase-3, -8 and -9 and the cleavage of PARP in HL-60. CA also activated Bid and Bax, leading to the loss of mitochondrial membrane potential (Δψ_m) and cytochrome c release into the cytosol, whereas Bcl-2 and Bcl-xL were unaffected by CA. These results suggest that CA has an anti-proliferative effect on leukemia cells via the induction of apoptosis mediated by mitochondrial dysfunction and caspase activation. CA may be a potential chemotherapeutic agent for the treatment of human leukemia.     

Development of a reduction-responsive amino acid that induces peptide bond cleavage in hypoxic cells

Hypoxia-responsive amino acids are indispensable in the preparation of hypoxic tumor-specific peptidyl prodrugs. In this paper, the design and synthesis of a reduction-responsive amino acid that induces peptide bond cleavage after reduction of the nitro group are described. Application to hypoxia-responsive peptide bond cleavage system is also reported.     

Fabrication of a DNA-lipid-apatite composite layer for efficient and area-specific gene transfer

A surface-mediated gene transfer system using biocompatible apatite-based composite layers has great potential for tissue engineering. Among the apatite-based composite layers developed to date, we focused on a DNA-lipid-apatite composite layer (DLp-Ap layer), which has the advantage of relatively high efficiency as a non-viral system. In this study, various lipid transfection reagents, including a newly developed reagent, polyamidoamine dendron-bearing lipid (PD), were employed to prepare the DLp-Ap layer, and the preparation condition was optimized in terms of efficiency of gene transfer to epithelial-like CHO-K1 cells in the presence of serum. The optimized DLp-Ap layer derived from PD had the highest gene transfer efficiency among all the apatite-based composite layers prepared in this study. In addition, the optimized DLp-Ap layer demonstrated higher gene transfer efficiency in the presence of serum than the conventional particle-mediated systems using commercially available lipid transfection reagents. It was also shown that the optimized DLp-Ap layer mediated the area-specific gene transfer on its surface, i.e., DNA was preferentially transferred to the cells adhering to the surface of the layer. The present gene transfer system using the PD-derived DLp-Ap layer, with the advantages of high efficiency in the presence of serum and area-specificity, would be useful in tissue engineering.     

Ultrastructural analysis of buckwheat starch components using atomic force microscopy

Morphological and structural features of buckwheat starch granules and nanocrystals were examined using atomic force microscopy and dynamic light scattering. Partially digested starch granules revealed a clear pattern of growth rings with the central core revealing lamellar structure. Atomic force microscopy and dynamic light scattering experiments revealed that the buckwheat starch granules were polygonal in shape and were in the range of 2 to 19 μm in diameter. The optimized acid hydrolysis process produced nanocrystals with the shape of spherical structure with lengths ranging from 120 to 200 nm, and the diameter from 4 to 30 nm from aqueous suspensions of buckwheat starch solution. The sorption isotherms on buckwheat starch nanocrystal/glycerol composite exhibited a 3-stage transition of moisture in the blending. The biocompatible nature of buckwheat starch nanocrystals and their structural properties make them a promising green nanocomposite material. PRACTICAL APPLICATION: Buckwheat starches had never been studied on a nanoscale, but we have achieved new understanding of starch granule morphology and concentric growth rings using nanoscale imaging. Since buckwheat is an underutilized crop, we foresee the potential application of buckwheat starch, starch-based nanocrystals, and nanoparticles, to expand markets and encourage producers to expand their buckwheat acreage. The atomic force image analysis suggests that buckwheat starch could be used as a new biopolymer material in food industries.     

The changes of transesterification level in PET/PEN blends with the addition of PET–PEN copolymer

The extent of transesterification in poly(ethylene terephthalate) (PET)/poly(ethylene‐2,6‐naphthalate) (PEN) blends with the addition of PET–PEN copolymers was examined by DSC and ¹H‐NMR measurements to evaluate the factor affecting the reaction level at a given temperature and time. Both block (P(ET‐block‐EN)) and random (P(ET‐ran‐EN)) copolymers were used as the copolymers. At a given treatment temperature and time, the level was increased by the addition of P(ET‐block‐EN) into PET/PEN blends. On the other hand, a reverse change was observed when P(ET‐ran‐EN) was mixed with PET/PEN blends. During the treatment, an inhomogeneous phase of the blends changed into the homogeneous one; however, the change showed little effect on the reaction level. The effects of molecular weight on the reaction level were also examined. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

On the combination of sulphite with food ingredients (aldehydes, ketones and sugars). II.

Summary Three kinds of combined sulphites (bisulphite adducts of acetaldehyde, pyruvic acid and D-mannose), different in combination strength, were prepared to provide a model system for comparative studies on the accuracy of several determination methods for combined sulphites. The purity of the combined sulphites, obtained either as crystals or amorphous powder, was shown to be not less than 99%.Five methods, formerly applied on the determination of residual sulphites in foods, were subjected to the determination of these combined sulphites. A modified Monier-Williams method, iodimetry and distillation-colorimetry were effective for the determination of combined sulphite, whilst a microdiffusion method and direct colorimetry (by use of mercuric chloride) were shown to be inadequate for the determination of combined sulphite.Three combined sulphites were shown to be produced by the reaction between free sulphite and acetaldehyde, pyruvic acid or D-mannose at room temperature within a short time in the weak acid to slightly alkaline pH range. About 50% of combined sulphite were produced by the reaction of equimolar amounts of sodium bisulphite and acetaldehyde or pyruvic acid.

---

Über die Bindung des Sulfits an Lebensmittelbestandteilen (Aldehyde, Ketone und Zucker). II.

Zusammenfassung Es wird die Darstellung der Bisulfit-Anlagerungsverbindungen von Acetaldehyd, Brenztraubensäure undd-Mannose beschrieben. Die Reinheit der gen. Verbindungen beträgt 99%.fünfAn Hand dieser Verbindungen wird überprüft, welche von fünf Standardmethoden zur Sulfitbestimmung in Lebensmitteln für die Bestimmung des gebundenen Sulfits geeignet ist. Hierbei ergeben die abgeänderte Monier-Williams-Methode, die Jodometrie und die Wasserdampfdestillation/Colorimetrie befriedigende Ergebnisse, während die Mikrodiffusion und die direkte Colorimetrie ungeeignet erscheinen.Die gen. Anlagerungsverbindungen bilden sich bei Zimmertemperatur im schwach sauren bis schwach alkalischen Milieu innerhalb kurzer Zeit. In einer äquimolaren Lösung aus Acetaldehyd bzw. Brenztraubensäure und Natriumhydrogensulfit liegt nach kurzer Zeit 50% des Sulfits als Anlagerungsverbindung vor.

---

---

Studies on the Analyses of Sulphites in Food (II)